EP3898913A1 - Verfahren zur herstellung von metal organic frameworks - Google Patents
Verfahren zur herstellung von metal organic frameworksInfo
- Publication number
- EP3898913A1 EP3898913A1 EP19829508.1A EP19829508A EP3898913A1 EP 3898913 A1 EP3898913 A1 EP 3898913A1 EP 19829508 A EP19829508 A EP 19829508A EP 3898913 A1 EP3898913 A1 EP 3898913A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- mil
- mixtures
- mof
- alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000012621 metal-organic framework Substances 0.000 title abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000013291 MIL-100 Substances 0.000 claims abstract description 18
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000003599 detergent Substances 0.000 claims description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 239000012459 cleaning agent Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229960004063 propylene glycol Drugs 0.000 claims description 7
- 235000013772 propylene glycol Nutrition 0.000 claims description 7
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- 229940035437 1,3-propanediol Drugs 0.000 claims description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 3
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 claims description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 2
- 229960005150 glycerol Drugs 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000004753 textile Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 230000035943 smell Effects 0.000 description 8
- 239000003945 anionic surfactant Substances 0.000 description 7
- 235000019645 odor Nutrition 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 208000035985 Body Odor Diseases 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000002845 discoloration Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000002304 perfume Substances 0.000 description 6
- 210000004243 sweat Anatomy 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 206010040904 Skin odour abnormal Diseases 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 238000004438 BET method Methods 0.000 description 3
- 239000004367 Lipase Substances 0.000 description 3
- 102000004882 Lipase Human genes 0.000 description 3
- 108090001060 Lipase Proteins 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000004851 dishwashing Methods 0.000 description 3
- 239000002979 fabric softener Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 125000005647 linker group Chemical group 0.000 description 3
- 235000019421 lipase Nutrition 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 2
- 102000013142 Amylases Human genes 0.000 description 2
- 108010065511 Amylases Proteins 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 102000005575 Cellulases Human genes 0.000 description 2
- 108010084185 Cellulases Proteins 0.000 description 2
- RKWGIWYCVPQPMF-UHFFFAOYSA-N Chloropropamide Chemical compound CCCNC(=O)NS(=O)(=O)C1=CC=C(Cl)C=C1 RKWGIWYCVPQPMF-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 102000035195 Peptidases Human genes 0.000 description 2
- 108091005804 Peptidases Proteins 0.000 description 2
- 239000004365 Protease Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000019418 amylase Nutrition 0.000 description 2
- 229940025131 amylases Drugs 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920005646 polycarboxylate Polymers 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 sulfanyl alcohols Chemical class 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- RGRNSTGIHROKJB-UHFFFAOYSA-N 3-hydroxy-3-methylhexanoic acid Chemical compound CCCC(C)(O)CC(O)=O RGRNSTGIHROKJB-UHFFFAOYSA-N 0.000 description 1
- GUJVUHKZVMVQDM-UHFFFAOYSA-N 3-methyl-1-sulfanylhexan-1-ol Chemical compound CCCC(C)CC(O)S GUJVUHKZVMVQDM-UHFFFAOYSA-N 0.000 description 1
- STBOKQUWWUFPAZ-UHFFFAOYSA-N 5-methoxycarbonylbenzene-1,3-dicarboxylic acid Chemical compound COC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 STBOKQUWWUFPAZ-UHFFFAOYSA-N 0.000 description 1
- 206010006326 Breath odour Diseases 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000002386 air freshener Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- ZOQOMVWXXWHKGT-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1.OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 ZOQOMVWXXWHKGT-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- PASOAYSIZAJOCT-UHFFFAOYSA-N butanoic acid Chemical compound CCCC(O)=O.CCCC(O)=O PASOAYSIZAJOCT-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 206010016766 flatulence Diseases 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 208000002557 hidradenitis Diseases 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000021190 leftovers Nutrition 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- SXBRULKJHUOQCD-UHFFFAOYSA-N propanoic acid Chemical compound CCC(O)=O.CCC(O)=O SXBRULKJHUOQCD-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 244000005714 skin microbiome Species 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0068—Deodorant compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/168—Organometallic compounds or orgometallic complexes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/12—Soft surfaces, e.g. textile
Definitions
- the present invention relates to a method for producing metal organic frameworks (MOF).
- Body odor is the term used to refer to all smellable body odors from people through the skin and also in a broader sense from other openings in the body, such as bad breath, or odors caused by excrement (urine, faeces, flatus). The clearest
- the smell of sweat is usually noticeable, whereby only the secretions of the apocrine sweat glands, which are mainly in the armpits, smell.
- Unsaturated or hydroxylated-branched fatty acids such as 3-methyl-2-hexanoic acid or 3-hydroxy-3-methylhexanoic acid, or sulfanyl alcohols, such as 3-methyl-sulfanylhexane-1-ol, are primarily responsible for body odor, especially for the smell of sweat.
- hydroxylated-branched fatty acids such as 3-methyl-2-hexanoic acid or 3-hydroxy-3-methylhexanoic acid
- sulfanyl alcohols such as 3-methyl-sulfanylhexane-1-ol
- Body odor itself is influenced by different bacteria that represent the skin flora. These form so-called lipases, which break down the fatty acids into smaller molecules, for example butanoic acid (butyric acid). Propanoic acid (propionic acid) is also a common component of sweat. It arises when amino acids are broken down by so-called propanoic acid bacteria.
- malodors In addition to body odor, other odors which humans perceive as unpleasant are also referred to as malodors in the present invention, such as those from
- Metal organic frameworks are scaffolds that consist of metal centers (atoms or clusters) and organic bridge molecules (linkers) as a connecting element between the metal centers.
- MOFs can in principle be two-dimensional or three-dimensional, in the present invention the MOFs with three-dimensional, porous networks are preferably present.
- MOFs are coordination polymers.
- Pore size of the MOFs vary.
- the pores are so large that they enclose the molecules which are responsible for the malodour.
- Preparations such as detergents or cleaning agents, are incorporated into the pores However, they should not be so large that they include effective components of the corresponding preparation, in the case of washing or cleaning agents, for example surfactants, and thus reduce the effectiveness.
- MOFs which have at least two carboxylic acid groups (COOH groups) are particularly preferred.
- Ligands of the HOOC-A-COOH type are preferred, where A is selected from
- the ligand (organic bridge molecule, linker) of the MOF is preferably selected from the following general formula (IV)
- R 1 , R 2 , R 3 and R 4 in the general formula (IV) independently of one another are -H, -COOH, - COO-, -OH or -NH2.
- the organic ligand of the MOF is particularly preferably selected from 1,4-benzenedicarboxylic acid (BDC), 1,3,5-benzenetricarboxylic acid (BTC), 2-amino-1,4-benzenedicarboxylic acid (ABDC),
- Fumaric acid its mono- or trivalent anions or mixtures thereof.
- an MOF can have several different organic ligands or only one organic ligand.
- the MOF preferably comprises aluminum, titanium, zirconium, iron, zinc, bismuth or oxocluster, hydroxocluster, hydroxyoxocluster or
- the MOF particularly preferably comprises aluminum and / or iron.
- MOF metals other than those mentioned often lead to discoloration of textiles should they come into contact with the so-called MOF. Therefore, in particular when using the MOFs in detergent, which are used for washing textiles, it is preferred if aluminum and / or iron are used as the metallic component. It has been shown that copper in particular leads to a discoloration of textiles and also to a coloration of rough surfaces, so that according to the invention the MOF is preferably free of copper.
- MOF-100 MIL-100 (AI), in which aluminum serves as the metal center and trimesic acid (1,3,5-benzenetricarboxylic acid) as the inorganic ligand. So far, this MOF has been obtained in a synthesis that requires high temperatures and pressures. In addition, the previously required use of nitric acid leads to a yellowish discoloration of the product obtained, and in the implementation of the
- T rimesic acid precursors Trimesic acid methyl ester releases toxic methanol. Furthermore, due to the drastic reaction conditions, the nitrate is partially decomposed with the formation of harmful nitrous gases. After the synthesis, the product is colored deep yellow, presumably by nitrated by-products, and also contains residues of unreacted trimesic acid, which is enclosed in the pores of the framework connection. Therefore, a complex washing process with N, N-dimethylformamide (DMF) must be connected to the synthesis, which is followed by a further washing process with water in order to remove the DMF again. Even after repeating this washing process several times, a yellowish-gray residual color of the product obtained in this way remains. Impurities from foreign crystallites are also not completely removed in this way.
- N, N-dimethylformamide DMF
- MIL-100 Al
- a production process for MIL-100 (Al) in which aluminum nitrate and trimesic acid are reacted in an alcohol / water mixture as the reaction medium, using NH3 and / or an NH3-releasing compound as a base for deprotonating the Trimesic acid acts, can be carried out at reaction temperatures below 200 ° C.
- the present application therefore relates to a process for the preparation of MIL-100 (Al), in which aluminum nitrate and trimesic acid are reacted in an alcohol / water mixture under the action of a base selected from NH3, an NH3-releasing compound or mixtures thereof .
- Ammonia itself and ammonia-releasing compounds can be used as bases.
- the group consisting of urea, urotropin, ammonium carbamate and mixtures thereof is particularly preferred, in particular urea.
- an alcohol / water mixture serves as the solvent.
- Suitable alcohols are, for example, the C2-6-alkylene glycols and poly-C2-3-alkylene glycol ethers, optionally etherified on one side with a Ci-e-alkanol, with an average of 1 to 9 identical or different, preferably identical, alkylene glycol groups per molecule, as well as C1-6 alcohols.
- Mono- or polyhydric Ci-e alcohols are particularly preferred, preferably selected from the group comprising methanol, ethanol, propanol, isopropanol, ethylene glycol,
- the alcohol is a polyhydric alcohol or a mixture of polyhydric alcohols.
- a polyhydric alcohol selected from the group consisting of glycerol, 1,2-propanediol, 1,3-propanediol and mixtures thereof is particularly preferably used, glycerol and 1,2-propanediol and mixtures thereof being very particularly preferred.
- the alcohol and the water are preferably used in a ratio of 98: 2 to 20:80, preferably 80:20 to 40:60 vol .-% at room temperature.
- reaction be carried out under mild conditions. It is therefore preferred if a reaction temperature is set below 200 ° C., preferably below 160 ° C.
- the MOF produced with the method according to the invention can be washed or
- Detergents preferably in amounts of 0.001 to 10% by weight, preferably 0.01 to 7% by weight, in particular 0.01 to 5% by weight, preferably 0.25 to 2.5% by weight and more preferably from 0.5 to 1% by weight. It has been shown that an increase in MOF does not contribute to a reduction in malodor. However, a proportion of 0.001% by weight is necessary in order to achieve an effect. Particularly good effects are achieved if MOF is contained in a proportion of 0.01% by weight or more and in particular at least 0.25% by weight. Larger portions of MOF can have a better effect, but they also result in higher costs. With a proportion of 10% by weight, a good one
- Odor reduction or prevention can be achieved. A proportion of 1% by weight also leads to a significant reduction in undesirable odors.
- the MOF produced according to the invention are preferably as particles in washing or
- the particle size is preferably 0.5 to 100 pm, in particular 5 to 70 pm, particularly preferably 10 to 50 pm. If the MOF are in the form of nanoparticles, there is a risk, particularly in the case of detergents, that only a small proportion is deposited on the substrate and thus used, while the majority is flushed away unused. If the particle size is larger than 100 pm, they are visible to the human eye. The MOF is deposited on the surface treated with the detergent or cleaning agent. Accordingly, they would be recognizable as contamination on the treated textile surface if they had a size of 100 pm or more. The particle size is therefore preferably less than 75 pm and in particular less than 50 pm.
- Detergents and cleaning agents can be used in the MOF produced according to the invention preferably in an amount of 0.001 to 10% by weight, preferably 0.01 to 7% by weight, in particular 0.01 to 5% by weight, preferably 0 Contain 25 to 2.5 wt .-% and more preferably from 0.5 to 1 wt .-%.
- a specific surface which is in the range from 100 to 4000 m 2 / g, is particularly suitable for storing off-odors, but without affecting the effectiveness to influence the cleaning of the washing or cleaning agents according to the invention.
- the specific surface is determined using the single-point BET method in accordance with DIN ISO 9277: 2014.
- the specific surface area is preferably 500 to 3200 m 2 / g and in particular 800 to 3000 m 2 / g.
- the washing and cleaning agents in which the MOF can be used include, in particular, household cleaners, washing, cleaning or pre-treatment agents or
- Refreshing sprays for textiles, fabric softeners, cosmetic products or air care products for example room sprays or air fresheners.
- Household cleaners for the purposes of this application are, for example, cleaning agents for cleaning hard surfaces,
- Registration are products for the cosmetic treatment of skin and hair
- Hair treatment agents such as hair shampoos
- Hair rinses, cures, conditioners, agents for bleaching, dyeing or shaping the hair such as colorants, bleaches, tinting agents, color fixing agents, waving agents or styling preparations such as hair setting agents, foaming agents or styling gels, shower gels, body creams, lotions,
- the MOF is preferably incorporated in the form of a dispersion; further preferably at least one dispersing aid and at least one
- the MOF can then be used as an aerosol directly on particularly odor-critical areas of textiles, for example the armpit area of
- Anionic surfactants such as preferably alkylbenzenesulfonate or alkyl sulfate, in particular in a proportion of 5 to 30% by weight, an anionic surfactant or mixtures of different anionic surfactants may be present,
- nonionic surfactants such as preferably fatty alcohol polyglycol ether, alkyl polyglucoside or fatty acid glucamide, for example 0.5 to 15% by weight of one or more nonionic surfactants,
- one or more builders such as zeolite, polycarboxylate or
- Sodium citrate in amounts of in particular 0 to 70% by weight, advantageously 5 to 60% by weight, preferably 10 to 55% by weight, in particular 15 to 40% by weight, one or more alkaline compounds, such as sodium carbonate, in particular in amounts of 0 to 35% by weight, advantageously 1 to 30% by weight, preferably 2 to 25% by weight, in particular 5 to 20% by weight,
- bleaching agents such as sodium perborate or sodium percarbonate
- one or more corrosion inhibitors for example sodium silicate
- one or more corrosion inhibitors for example sodium silicate, for example in amounts from 0 to 10% by weight, advantageously from 1 to 6% by weight, preferably from 2 to 5% by weight, in particular from 3 to 4% by weight
- one or more stabilizers for example phosphonates, advantageously in a proportion of 0 to 1% by weight
- one or more foam inhibitors for example soap, silicone oils, paraffins, advantageously in a proportion of 0 to 4% by weight, preferably 0.1 to 3% by weight, in particular 0.2 to 1% by weight,
- Enzymes for example proteases, amylases, cellulases, lipases, advantageously in a proportion of 0 to 2% by weight, preferably 0.2 to 1% by weight, in particular 0.3 to 0.8% by weight ,
- Graying inhibitor for example carboxymethyl cellulose, advantageously in a proportion of 0 to 1% by weight,
- Discoloration inhibitor for example polyvinylpyrrolidone derivatives, advantageously in a proportion of 0 to 2% by weight,
- Adjusting agents for example sodium sulfate, advantageously in a proportion of 0 to 20% by weight,
- optical brighteners such as stilbene derivative, biphenyl derivative, advantageously in a proportion of 0 to 0.4% by weight, in particular 0.1 to 0.3% by weight,
- fragrances such as perfume oils
- the information is given in% by weight and relates to the total weight of the
- the MOFs produced by the process according to the invention can also be used in liquid or gel detergents.
- Preferred liquid washing or cleaning agents have a water content, in particular of 3 to 95% by weight, preferably of 8 to 80% by weight and in particular of 25 to 70% by weight, based on the
- the water content can also be lower and be 30% by weight or less, preferably 20% by weight or less, in particular 15% by weight or less.
- the data in% by weight are also based here on the total weight of the composition.
- the liquid agents can also contain other non-aqueous solvents.
- a preferred liquid, in particular gel-like detergent can preferably comprise components which are selected from the following:
- anionic surfactants such as preferably alkylbenzenesulfonate, alkyl sulfate, in particular in a proportion of 5 to 40% by weight, an anionic surfactant or mixtures of different anionic surfactants can be present,
- nonionic surfactants such as preferably fatty alcohol polyglycol ether, alkyl polyglucoside, fatty acid glucamide, preferably in amounts of 0.5 to 25% by weight of one or more nonionic surfactants,
- one or more builders such as zeolite, polycarboxylate, sodium citrate, advantageously in a proportion of 0 to 15% by weight, preferably 0.01 to 10% by weight, in particular 0.1 to 5% by weight ,
- foam inhibitors for example soap, silicone oils, paraffins, preferably in amounts of 0 to 10% by weight, advantageously 0.1 to 4% by weight, preferably 0.2 to 2% by weight, in particular 1 to 3% by weight,
- Enzymes such as proteases, amylases, cellulases, lipases, preferably in amounts of 0 to 3% by weight, advantageously 0.1 to 2% by weight, preferably 0.2 to 1% by weight, in particular 0 , 3 to 0.8% by weight, optical brighteners, for example stilbene derivative, biphenyl derivative, in particular in amounts from 0 to 1% by weight, advantageously from 0.1 to 0.3% by weight, in particular from 0.1 to 0.4% by weight %,
- fragrances such as perfume oils
- optionally soap in particular from 0 to 25% by weight, advantageously from 1 to 20% by weight, preferably from 2 to 15% by weight, particularly from 5 to 10% by weight, optionally non-aqueous solvents, in particular alcohols, advantageously from 0 to 25% by weight, preferably from 1 to 20% by weight, in particular from 2 to 15% by weight.
- optionally non-aqueous solvents in particular alcohols, advantageously from 0 to 25% by weight, preferably from 1 to 20% by weight, in particular from 2 to 15% by weight.
- the data in% by weight relate to the total weight of the washing or
- the MOFs can also be incorporated into liquid fabric softeners, which may additionally preferably contain further components which are selected from the following: cationic surfactants, such as in particular esterquats, preferably in amounts of 5 to 30% by weight,
- Cosurfactants such as, for example, glycerol monostearate, stearic acid, fatty alcohols,
- Fatty alcohol ethoxylates in particular in amounts of 0 to 5% by weight, preferably 0.1 to 4% by weight,
- Emulsifiers such as fatty amine ethoxylates, in particular in amounts of 0 to 4
- fragrances such as perfume oils
- Solvents such as water in particular, in amounts of preferably 60 to 90% by weight.
- the percentages by weight relate in each case to the total weight of the formulation, that is to say the fabric softener.
- the specification in ppm relates to the weight (ppm by weight).
- Example 1 Synthesis of MIL-100 (AI) in 68 vol .-% 1,2-propanediol / water mixture at 100 ° C / 48h on a 101 scale
- the stirred kettle was then drained and the contents centrifuged to separate the solid from the mother liquor.
- the crude product was suspended in ethanol, stirred for 30 minutes, centrifuged again and then extracted with ethanol in a Soxhlet apparatus. Then the solid was first dried for 8 hours at 80 ° C. in a forced-air drying cabinet and then activated at 150 ° C. overnight in vacuo (10 3 mbar).
- the X-ray powder diffractogram of the sample shows the reflections of MIL-100 (AI) at the expected positions; apart from MIL-100 (AI), no other crystalline phase can be seen (upper graph: synthesis, lower graph: theory).
- Example 2 Synthesis of MIL-100 (AI) in 58 vol .-% glycerol / water mixture at 100 ° C / 48h on a 101 scale
- the specific surface of the product was 1320 mz / g, the pore volume was 0.79 cnTYg.
- Example 3 Synthesis of MIL-100 (AI) in 68 vol .-% 1, 2-propanediol / water mixture at 100 ° C / 48h on a 20I scale with a higher concentration of raw materials 494.4 g (1317.9 mmol) of Al (Nq3) 3 .9 H 2 O together with 66.0 g (1098.9 mmol) of urea in 2 l of dist. Water dissolved. 11.6 l of propanediol together with 6.4 l of water were placed in a stirred kettle and preheated to 65.degree. C. while stirring (280 rpm). After adding the aqueous
- the stirred kettle was then drained and the contents centrifuged to separate the solid from the mother liquor.
- the crude product was suspended in ethanol, stirred for 30 minutes, centrifuged again and then extracted with ethanol in a Soxhlet apparatus. Then the solid was first dried for 8 hours at 80 ° C. in a forced-air drying cabinet and then activated at 150 ° C. overnight in vacuo (10 -3 mbar).
- the X-ray powder diffractogram of the sample shows the reflections of MIL-100 (AI) at the expected positions; apart from MIL-100 (AI), no other crystalline phase can be seen (upper graph: synthesis, lower graph: theory).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102018222193.6A DE102018222193A1 (de) | 2018-12-18 | 2018-12-18 | Verfahren zur Herstellung von Metal Organic Frameworks |
PCT/EP2019/085780 WO2020127368A1 (de) | 2018-12-18 | 2019-12-17 | Verfahren zur herstellung von metal organic frameworks |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3898913A1 true EP3898913A1 (de) | 2021-10-27 |
EP3898913B1 EP3898913B1 (de) | 2023-07-05 |
Family
ID=69063755
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19829508.1A Active EP3898913B1 (de) | 2018-12-18 | 2019-12-17 | Verfahren zur herstellung von metal organic frameworks |
Country Status (4)
Country | Link |
---|---|
US (1) | US20210309937A1 (de) |
EP (1) | EP3898913B1 (de) |
DE (1) | DE102018222193A1 (de) |
WO (1) | WO2020127368A1 (de) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102022108117A1 (de) | 2022-04-05 | 2023-10-05 | Henkel Ag & Co. Kgaa | Einsatz von mof in wc-produkten zur beseitigung von schlechtgerüchen |
CN114957691B (zh) * | 2022-05-25 | 2023-02-14 | 华南理工大学 | 一种用于碳捕获的小分子配体修饰MOFs吸附剂的制备方法 |
DE102022121763A1 (de) | 2022-08-29 | 2024-02-29 | Henkel Ag & Co. Kgaa | Einsatz von metallorganischen gerüstverbindungen in wc-produkten zur beseitigung von schlechtgerüchen |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102011076080A1 (de) * | 2011-05-18 | 2012-11-22 | Technische Universität Dresden | Verfahren zur Herstellung von Partikeln enthaltend Metall-organische Gerüstverbindungen |
DE102015211920A1 (de) * | 2015-06-26 | 2016-12-29 | Henkel Ag & Co. Kgaa | Wasch- oder Reinigungsmittel zur Verringerung von Fehlgerüchen |
DE102017209840A1 (de) * | 2017-06-12 | 2018-12-13 | Henkel Ag & Co. Kgaa | Triggerspray zur Beseitigung von Schlechtgeruch und Deoflecken |
-
2018
- 2018-12-18 DE DE102018222193.6A patent/DE102018222193A1/de not_active Withdrawn
-
2019
- 2019-12-17 EP EP19829508.1A patent/EP3898913B1/de active Active
- 2019-12-17 WO PCT/EP2019/085780 patent/WO2020127368A1/de unknown
-
2021
- 2021-06-18 US US17/351,648 patent/US20210309937A1/en active Pending
Also Published As
Publication number | Publication date |
---|---|
US20210309937A1 (en) | 2021-10-07 |
EP3898913B1 (de) | 2023-07-05 |
WO2020127368A1 (de) | 2020-06-25 |
DE102018222193A1 (de) | 2020-06-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0556660B1 (de) | Verwendungen von alpha-Hydroxyfettsäuren | |
EP1257353B1 (de) | Wasch- oder reinigungsmittel mit komponenten in form von mikro- und/oder nanokapseln | |
EP3898913B1 (de) | Verfahren zur herstellung von metal organic frameworks | |
DE69920167T2 (de) | Antimikrobielle duftende zusammensetzungen | |
WO2016207385A1 (de) | Wasch- oder reinigungsmittel zur verringerung von fehlgerüchen | |
DE60121939T2 (de) | Verwendung von amino benzoesäuren in zusammensetzungen mit duftstoffen | |
DE60035639T2 (de) | Hydroxydiphenyletherverbindungen | |
EP1262170B1 (de) | Zusammensetzungen, enthaltend quaternäre Ammoniumverbindungen | |
EP1262171A1 (de) | Neuartig konfektionierte quaternäre Ammoniumzusammensetzungen | |
DE10129225A1 (de) | Neuartig konfektionierte quaternäre Ammoniumverbindungen | |
DE69428788T2 (de) | Parfumzusammensetzung | |
DE3730444A1 (de) | Weichspuelmittel | |
DE3686887T2 (de) | Verfahren zum neutralisieren des unangenehmen achselgeruches. | |
CH668966A5 (de) | N-hoehere alkyl- bzw. alkenylneoalkanamide sowie verfahren zu deren herstellung. | |
EP0082299A1 (de) | Triamin-trioxide, Verfahren zu deren Herstellung und diese enthaltende Reinigungsmittel | |
EP2925842B1 (de) | Duftstoffmischungen enthaltend hexylsalicylat | |
DE3839769A1 (de) | Oberflaechenaktive mischungen | |
EP1103180B1 (de) | Hydroxyphenylvinylthiazole | |
WO2000007446A1 (de) | Mikrobizide wirksubstanzen | |
DE19640086C2 (de) | Festes Detergenzgemisch, dessen Herstellung und Verwendung | |
DE1619182B2 (de) | Verfahren zum weichmachen von textilien | |
DE2357278B2 (de) | Ampholyte, Verfahren zu ihrer Herstellung und diese enthaltende Wasch-, Reinigungs- und Desinfektionsmittel | |
EP1191016B1 (de) | Neue Diquaternäre Ammoniumverbindungen | |
WO2001075213A1 (de) | Verwendung vom 3-iod-2-propinyl-carbamaten als antimikrobieller wirkstoff | |
DE1947745C (de) | Antimikrobielle grenzfachenaktive Mittel |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20210610 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20220630 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20230221 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230531 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1584862 Country of ref document: AT Kind code of ref document: T Effective date: 20230715 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 502019008439 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG9D |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20230705 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230705 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20231006 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230705 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20231105 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230705 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230705 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20231106 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20231005 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230705 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230705 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20231105 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230705 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20231006 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230705 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230705 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20231214 Year of fee payment: 5 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230705 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502019008439 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230705 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230705 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230705 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230705 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230705 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230705 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230705 |
|
26N | No opposition filed |
Effective date: 20240408 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230705 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20231217 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230705 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20231217 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20231231 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230705 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20231217 |